Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/0827—Developers with toner particles characterised by their shape, e.g. degree of sphericity
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature

Definitions

• the present invention relates to a dry toner used for electrophotography, electrostatic recording, electrostatic printing, and the like. ⁇ Background technology>
• a dry toner used for electrophotography, electrostatic recording, electrostatic printing, and the like a toner binder such as a styrene-based resin or polyester that has been melt-kneaded with a coloring agent and the like and finely pulverized has been used.
• toners After these dry toners are developed and transferred to paper or the like, they are fixed by heating and melting using a hot roll. At that time, if the temperature of the hot roll is too high, the toner melts excessively, and a problem of hot-rolling occurs. On the other hand, if the temperature of the heat roll is too low, the toner does not melt sufficiently and the fixing becomes insufficient. From the viewpoint of energy saving and miniaturization of copiers and other devices, toners having a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixing property) are required.
• hot offset resistance hot offset resistance
• fixing temperature low temperature fixing property
• the toner needs to have a lower melt viscosity because of the necessity for the glossiness and color mixing of the image, and a sharp-melting polyester toner is required.
• a binder is used. Hot offset is likely to occur with such a toner, and therefore, in the case of full-color equipment, it has been customary to apply a silicone oil or the like to a heat roll.
• the toners disclosed in (1) and (2) are not yet compatible with heat-resistant storage stability and low-temperature fixability, and cannot be used in full-color applications because they do not exhibit gloss.
• the toner disclosed in (3) has insufficient low-temperature fixability and the hot offset property in oilless fixation is not satisfactory.
• the toner disclosed in (1) has the effect of improving powder fluidity and transferability, it has insufficient low-temperature fixability and has a problem that much energy is required for fixing. This problem is particularly remarkable in full-color toners.
• the toner disclosed in 5 also has the effect of improving powder fluidity and transferability, but is superior to 4 in low-temperature fixability, but has insufficient hot offset resistance and is not suitable for hot rolls. It is not something that makes it unnecessary to apply oil to the surface.
• An object of the present invention is to provide a dry toner excellent in powder fluidity and transferability when a small particle size toner is used.
• Another object of the present invention is to provide a dry toner excellent in all of heat resistance storage stability, low temperature fixability, and hot offset resistance.
• an object of the present invention is to provide a dry toner excellent in glossiness of an image when used in a full color copier or the like.
• a further object of the present invention is to provide a dry toner which does not require oil application to a hot roll.
• the present invention provides a dry toner comprising a toner binder and a colorant, wherein the toner has a practical sphericity of 0.91 to L.000, and the toner binder has a high sphericity.
• (MnA / MnB) is 1.6 or more, and the ratio (MwA / MwB) of the weight average molecular weight (MwA) of the resin (A) to the weight average molecular weight (MwB) of the resin (B) is 2 A dry toner characterized by the above.
• the practical sphericity of Wade 11 is (a circle equal to the projected area of a particle) Diameter) ⁇ (the diameter of the smallest circle circumscribing the projected image of the particle), which can be measured by observing the particle with an electron microscope.
• the practical sphericity of Wad 11 is usually 0.90 to: L. 0 °, preferably 0.95 to 1.00, and more preferably 0.98 to 1.00.
• the practical sphericity of all the toner particles need not be in the above range, but may be in the above range as a number average. The number average is calculated from the values measured by randomly extracting about 20 of the obtained toner particles.
• the particle size of the toner, the median diameter (d 50) is usually 2 to 2 preferably 3 to
• Examples of the high molecular weight condensed resin (A) and the low molecular weight condensed resin (B) that constitute the toner binder include polyester, polyurethane, polyurethane, polyamide, and epoxy resin. Among them, preferred are polyester, polyurethane and epoxy resin, and particularly preferred is polyester. Examples of the polyester include a polycondensate of a polyol (1) and a polycarboxylic acid (2).
• Examples of the polyol (1) include a diol (1-1) and a polyol having a valency of 3 or more (1-2). (1-1) alone, or (1-1) and a small amount of (1-2) Mixtures are preferred.
• the ratio of the mixture is usually from 100/0 to 100/20, preferably from 100/0 to 100/10, in a molar ratio of (1-1) to (1-2).
• C2-C18 alkylene glycols (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, dodecanediol, etc.
• Alkylene ether glycols having 4 to 1000 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols having 5 to 18 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.);
• Bisphenols having 12 to 23 carbon atoms bisphenol A, bisphenol F, bisphenol S, etc.
• Alkylene oxides having 2 to 18 carbon atoms e.g., ethylene oxide, propylene oxide, butylene oxide, hy-olefine oxide of the above alicyclic diols or bisphenols. 2 to 20).
• alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts having 2 to 18 carbon atoms of bisphenols are particularly preferred.
• bisphenols particularly, bisphenol A.
• the ratio of the alkylene oxide adduct of bisphenols is usually at least 30 mol%, preferably at least 50 mol%, particularly preferably at least 70 mol%.
• Polyhydric aliphatic alcohols having 3 to 8 or more valences (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); phenols having 3 to 8 or more valences (trisphenol PA, phenol novolak) , Cresol novolak, etc.);
• Examples of the above trivalent or higher polyphenols include alkylene oxide adducts having 2 to 18 carbon atoms (addition mole number is 2 to 20).
• polycarboxylic acid (2) examples include a dicarboxylic acid (2-1) and a polycarboxylic acid having a valency of 3 or more (2-2), and (2-1) alone and (2-1) and a small amount of ( Preference is given to mixtures of 2-2).
• the mixture ratio is the mole of (2-1) and (2-2) The ratio is usually from 100/0 to L00 / 20, preferably from 100/0 to LOO / 10.
• C2-C20 alkylenedicarboxylic acids succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, dodecenylsuccinic acid, dodecylsuccinic acid, etc.
• alkenylenedicarboxylic acids maleic acid, fumaric acid, etc.
• aromatic dicarboxylic acids Acids phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc.
• alkylene dicarboxylic acids having 4 to 20 carbon atoms especially adipic acid and dodecenyl succinic acid
• alkene diene dicarboxylic acids having 4 to 20 carbon atoms especially maleic acid and fumaric acid
• 8 carbon atoms especially 8 carbon atoms.
• ⁇ 20 aromatic dicarboxylic acids particularly isophthalic acid and terephthalic acid.
• Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
• the polycarboxylic acid (2) may be reacted with the polyol (1) using the above-mentioned acid anhydride or lower alkyl ester (eg, methyl ester, ethyl ester, isopropyl ester).
• acid anhydride or lower alkyl ester eg, methyl ester, ethyl ester, isopropyl ester.
• the ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/2 as a molar ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is from 1.5 / 1 to 1 / 1.5, more preferably from 1.3 / 1 to 1 / 1.3.
• the polycarboxylic acid and the polyol are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxy titanate and dibutyltin oxide to be dehydrated and condensed. Is obtained. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
• a polyester modified with a urethane bond and / or a urea bond is preferable.
• polyesters modified with urethane bonds include polyesters having a hydroxyl group, which are polycondensates of polyol (1) and polycarbonate (2), and polyisocyanate. —Reaction products with (3).
• the number of moles of the hydroxyl group in (1) is made to react more than the number of carboxyl groups in (2). And the like.
• Examples of the polyol (1) include the aforementioned diols (1-1) and tri- or higher valent polyols (1-2).
• Examples of the polycarboxylic acids (2) include dicarboxylic acids (2-1) and 3 Polycarboxylic acid (2-2) having a valency or higher.
• the ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [ ⁇ H] and the carboxyl group [COOH]. , Preferably 1.5 / 1 to 1/1, more preferably 1.3 / :! to 1.02 / 1.
• the number average molecular weight of the polyester having a hydroxyl group is usually from 1,000 to 20,000, preferably from 1500 to 15,000, particularly preferably from 2,000 to 10,000.
• the weight average molecular weight is usually 2,000 to 50,000, preferably 3,000 to 30,000, particularly preferably 4,000 to 20,000.
• the hydroxyl value of the polyester having a hydroxyl group is generally 5 to 120, preferably 7 to 70, and particularly preferably 10 to 60.
• the acid value is usually 10 or less, preferably 5 or less, particularly preferably 2 or less.
• polyisocyanate (3) examples include an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), an aliphatic polyisocyanate having 2 to 18 carbon atoms, and a carbon number of 4 To 15 alicyclic polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, and modified products of these polyisocyanates (urethane group, carpoimide group, arophanate group, urea group, Buret group, ⁇ retdione group, uretoimine group, isocyanurate group, oxazolidone group-containing variant) and mixtures of two or more of these.
• aromatic polyisocyanate examples include 1,3- and / or 1,4-phenylenediisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TD I), crude TDI, 2,4,1 and / or 4,4, diphenylmethanediisocyanate (MD I), crude MDI [crude diaminophenylmethane [formaldehyde and aromatic amine (aniline) or a mixture thereof] A mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight) of a polyamine having three or more functions] phosgenated product: polyallylpolyisocynate (PAP 1)], 1,5- Examples include naphthylene diisocyanate, 4,4,4 "-triphenylmethanetriisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate.
• aliphatic polyisocyanate examples include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, and 1,6. , 11-Dindecanetriisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate And bis (2-isocyanatoethyl) carbonate, 2-polyisocyanatoethyl-2,6-diisocyanatohexanoate, and other aliphatic polysocyanates.
• alicyclic polyisocyanate examples include isophorone diisocyanate (IPDI), dicyclohexylmethane 1,4,4,1-diisocyanate (hydrogenated MDI), and cyclohexylene diisocyanate.
• IPDI isophorone diisocyanate
• MDI dicyclohexylmethane 1,4,4,1-diisocyanate
• cyclohexylene diisocyanate 1, methylcyclohexylene didisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) 1,4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6 — Norbornane disocyanate and the like.
• araliphatic polyisocyanates include m- and / or p-xylylene diisocyanate (XDI), hi-a, hi-, hi-, mono-tetramethylxylylene diisocyanate (TMXDI) ).
• Modified products of the above polyisocyanates include modified MD I (urethane-modified MD I, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and other polyisocyanate modifications, and mixtures of two or more of these [eg, modified MDI and urethane-modified TDI] (Used in combination with (isocyanate-containing prepolymer)).
• aromatic polyisocyanates having 6 to 15 carbon atoms
• aliphatic polyisocyanates having 4 to 12 carbon atoms
• alicyclic polyisocyanates having 4 to 15 carbon atoms
• Particularly preferred are TD I, MD I, HD I, hydrogenated MD I, and IPDI.
• polyester having a hydroxyl group is reacted with the polyisocyanate (3), another polyol can be used in combination.
• the ratio of the polyisocyanate (3) is usually 1/2 to 2 as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the total [OH] of the polyester having a hydroxyl group and another polyol. / 1, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1. SZl l / l.2.
• the polyester modified by urethane bond can be produced by the following method.
• the polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C in the presence of a known esterification catalyst such as tetrabutoxythinate and dibutyltin oxide, and if necessary, the pressure is reduced.
• the generated water is distilled off while obtaining a polyester having a hydroxyl group.
• the polyisocyanate (3) and, if necessary, the polyol are reacted with each other to obtain a polyester modified with a urethane bond.
• a solvent can be used if necessary.
• Solvents that can be used include aromatic solvents (toluene, xylene, etc.); ketones (aceton, methylethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylform, etc.) Inactive to isocyanate (3) such as amide, dimethylacetamide, etc. and ethers (tetrahydrofuran, etc.).
• aromatic solvents toluene, xylene, etc.
• ketones aceton, methylethyl ketone, methyl isobutyl ketone, etc.
• esters ethyl acetate, etc.
• amides dimethylform, etc.
• Inactive to isocyanate (3) such as amide, dimethylacetamide, etc. and ethers (tetrahydrofuran, etc.).
• polyester prepolymer having an isocyanate group (a) examples include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen-containing group, and a polyisocyanate (3). Reaction products are exemplified.
• the active hydrogen-containing group contained in the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), a carboxyl group, and the like. Of these, an alcoholic hydroxyl group is preferable.
• the polyester having an alcoholic hydroxyl group can be obtained by using an excessive amount of polyol as in the case of the above-mentioned polyester modified with a urethane bond.
• a polyester having a carboxyl group can be obtained by excessively using a polycarboxylic acid.
• polystyrene resin examples include the same polyesters as those modified with urethane bonds, and preferred ones are also the same.
• the ratio of the polyisocyanate (3) is usually 5/1 to 1/1 as the equivalent ratio [NC ⁇ ] / [OH] of the isocyanate group [NCO] and the hydroxyl group [ ⁇ H] of the hydroxyl group-containing polyester. It is preferably from 4/1 to 1.271, and more preferably from 2.5 / 1 to 1.5 / 1.
• the NCO content (NCO equivalent) is usually from 500 to 100, preferably from 700 to 8,000, particularly preferably from 1,000 to 5,000.
• the amines (b) include diamine (b1), triamine or higher polyamine (b2), aminoamino alcohol (b3), aminomercapnone (b4), and amino acid (b5). And (b6) in which the amino group of (b1) to (b5) is blocked.
• diamine (bl) examples include aromatic diamines having 6 to 23 carbon atoms (phenylenediamine, getyltoluenediamine, 4,4 ′ diaminodiphenylmethane, etc.); alicyclic diamines having 5 to 20 carbon atoms ( 4,4, -diamino-1,3,3, dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc.); And aliphatic diamines having 2 to 18 carbon atoms (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.).
• Examples of the trivalent or hexavalent or higher polyamine (b 2) include diethylenetriamine and triethylenetetramine.
• Examples of the amino alcohol (b3) include those having 2 to 12 carbon atoms, and specific examples include ethanolamine and hydroxyethylaniline.
• Examples of the aminomercapone (b4) include those having 2 to 12 carbon atoms, and specific examples thereof include aminoethylmercapone and aminopropylmercapone.
• the amino acid (b5) includes those having 2 to 12 carbon atoms, and specific examples thereof include aminopropionic acid and aminocaproic acid.
• Examples of (b 6) in which the amino group of (b 1) to (b 5) is blocked include the amines of (b 1) to (b 5) and ketones having 3 to 8 carbon atoms (acetone, methylethyl ketone) , Methylisobutyl ketone, etc.), and oxazoline compounds.
• amines (b) are (b 1) (especially 4,4 ′ diaminodiphenylmethane, isophoronediamine and ethylenediamine) and mixtures of (b 1) with a small amount of (b 2) (especially diethylenetriamine). . More preferably, the amino groups of these amines are blocked.
• the ratio of the mixture is usually 100/0 to: L00 / 10, preferably 100/0 to: L00 / 5, in a molar ratio of (b1) and (b2).
• the molecular weight of the urea-modified polyester can be adjusted by using a reaction terminator.
• the reaction terminator include monoamines (such as getylamine, dibutylamine, butylamine, and laurylamine), and products thereof (ketimine compounds).
• the ratio of the amines (b) is calculated as the equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the prepolymer (a) having an isocyanate group and the amino group [NHx] in the amines (b). , Usually 1/2 to 2/1, preferably 1.5 / 1 L / l.5, more preferably 1.2 / 1 to 1 / 1.2.
• the polyester modified with the rare bond may contain a urethane bond together with the rare bond.
• the ratio of the rare bond to the urethane bond is usually 10/0 to 1/9, preferably 8/2 to 2/8, and more preferably 6/4 to 3/7.
• a polyester modified with a rare bond can be produced by the following method.
• a polyester having a hydroxyl group is obtained, and then a polyisocyanate (3) is reacted therewith at 40 to 140 ° C. to obtain a prepolymer having an isocyanate group. This is reacted with amines (or a block thereof) at 0 to 140 ° C to obtain a polyester modified with a rare bond.
• a solvent can be used if necessary. Examples of usable solvents include the same as described above.
• the polyurethane in the present invention include a polyadduct of a polyol (1) and a polyisocyanate (3).
• polyol (1) examples include the aforementioned diol (1-1) and tri- or higher valent polyol (112).
• polyisocyanate (3) examples include the above-described aromatic polyisocyanate having 6 to 20 carbon atoms (excluding the carbon in the NCO group, the same applies hereinafter), aliphatic polyisocyanate having 2 to 8 carbon atoms, L8 aliphatic polyisocyanate, C4 to C15 alicyclic polyisocyanate, C8 to C15 araliphatic polyisocyanate, and modified products of these polyisocyanates (urethane group, carbodiimide group, arophanate group, urea group, urea group) Group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product) and a mixture of two or more thereof.
• polyurea in the present invention include a reaction product of the polyisocyanate (3) and the amines (b).
• Examples of the amines (b) include the diamines (b1) described above, and trivalent or higher valent compounds. / 18 Polyamines (b 2), amino alcohols (b 3), amino mercapones (b 4), amino acids (b 5), and amino groups of (b 1) to (b 5) which are blocked ( b 6).
• (b) especially 4,4 ′ diamino diphenylmethane, isophorone diamine and ethylene diamine
• (b 1) especially 4,4 ′ diamino diphenylmethane, isophorone diamine and ethylene diamine
• (b 2) especially diethylene triamine
• Is a mixture of The mixture ratio is usually 100/0 to: L00 / 10, preferably 100/0 to: L00 / 5, in a molar ratio of (b1) and (b2).
• the molecular weight of polyurea can be adjusted by using a reaction terminator.
• the reaction terminator include monoamines (such as getylamine, dibutylamine, butylamine, and laurylamine), and those obtained by blocking them (ketimine compounds).
• the ratio of the amines (b) is determined by the molar ratio of the isocyanate group [N CO] in the polyisocyanate (3) and the amino group [NHx] in the amines (b) [NC ⁇ ] / [NH x] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.2 / 1 to 1 / 1.2.
• the molar ratio of the amino group in (b) to the total number of hydroxyl groups, mercapto groups or carboxyl groups [YHx] [NCO] / [ YHx] is usually 1/2 to 2/1, preferably 1.5 / 1 to 11.5, and more preferably 1.2 / 1 to 1 / 1.2.
• Polyamides include polycondensates of polycarboxylic acids (2) and amines (b).
• polycarboxylic acid (2) examples include the above-mentioned dicarboxylic acids (2-1) and tricarboxylic or higher polycarboxylic acids (2-2).
• the above-mentioned diamines (b 1) trivalent to hexavalent or higher Polyamines (b 2), amino alcohols (b 3), amino mercaptans (b 4), amino acids (b 5), and those obtained by blocking amino groups of (b 1) to (b 5) (b 6 ).
• Epoxy resins include addition condensation products of bisphenols (bisphenol A, bisphenol, bisphenol, etc.) with epichlorohydrin.
• the ratio (MnA / MnB) of the number average molecular weight of the high molecular weight resin (A) to the low molecular weight resin (B) must be 1.6 or more. It is preferably at least 1.9, more preferably 2.1-33, particularly preferably 2.3-28. If the value is less than 1.6, the hot offset resistance is insufficient when the low-temperature fixing property is improved, and the low-temperature fixing property is insufficient when the hot offset resistance is improved.
• the number average molecular weight (MnA) of the resin (A) is usually more than 5,000, preferably from 6,000 to 100,000, more preferably from 6500 to 60,000.
• the number average molecular weight (MnB) of the resin (B) is usually from 1,000 to 5,000, preferably from 1,300 to 4,000, more preferably from 1,500 to 3,500.
• the weight average molecular weight ratio (MwA / MwB) of the resin (A) and the resin (B) must be 2.0 or more. It is preferably from 2.5 to 100, more preferably from 4.0 to 70, particularly preferably from 5.0 to 50. If it is less than 2.0, the hot offset resistance is insufficient when the low-temperature fixing property is improved, and the low-temperature fixing property is insufficient when the hot offset resistance is improved.
• the weight average molecular weight (MwA) of the resin (A) is usually 5 000 or more, preferably 6000 to: L million, more preferably 8,000 to 500,000.
• the weight average molecular weight (MwB) of the resin (B) is usually from 1,000 to 50,000, preferably from 1,500 to 20,000, more preferably from 2,000 to 20,000.
• the weight ratio of the resin (A) to the resin (B) is usually 5/95 to 60/40, preferably 8/92 to 55/45, more preferably 10/90 to 50/50, particularly Like Or 15/85 to 40/60.
• the toner binder has at least two peaks in the molecular weight distribution measured by gel filtration chromatography (GPC).
• the molecular weight distribution obtained by GPC measurement has at least one peak in each of a region having a peak molecular weight of less than 20,000 and a region having a peak molecular weight of 30,000 or more.
• the molecular weight distribution was measured by preparing a calibration curve of molecular weight with standard polystyrene using tetrahydrofuran (hereinafter abbreviated as THF) as a solvent in gel permeation chromatography (hereinafter abbreviated as GPC). .
• THF tetrahydrofuran
• GPC gel permeation chromatography
• the specific conditions for measuring the molecular weight are as follows.
• HLC—802A made by Toyo Soda
• molecular weight calibration curve is based on standard polystyrene (molecular weights: 8.42 million, 4.48 million, 2.89 million, 109,000, 35.5 million, 190,000, 964,000, 3.790, 1.960, 9.1,000, 2. 98,000, 870, 500).
• the difference (SPA-SPB) between the SP value (SPA) of the high molecular weight condensed resin (A) and the SP value (SPB) of the low molecular weight condensed resin (B) constituting the toner binder is used.
• the SP value can be calculated by a known Fedors method.
• the glass transition point (T g) of the toner binder is usually from 35 to 85 ° C., preferably from 45 to 70 ° C., from the viewpoints of heat resistance storage stability and low-temperature fixability of the toner.
• the measuring frequency 20 H z in 1000 0 dyne / cm 2 and comprising a temperature (TG '), from the viewpoint of resistance to hot web offset resistance usually 100 ° C or higher, preferably 110 to 200 ° C.
• the temperature ( ⁇ 7) at which the viscosity of the toner binder becomes 1000 voids at a measurement frequency of 20 Hz is usually 180 ° C or less, preferably 90 to 60 ° C from the viewpoint of low-temperature fixability.
• TG ' is preferably higher than T7 ?, from the viewpoint of achieving both low-temperature fixing property and hot offset resistance.
• the difference (TG, - ⁇ ) between TG, and Tr? is preferably 0 ° C or more. It is more preferably at least 10 ° C, particularly preferably at least 20 ° C.
• the difference between ⁇ ? And Tg is preferably 100 ° C or less. It is more preferably at most 90 ° C, particularly preferably at most 80 ° C.
• dyes can be used as the colorant of the present invention.
• Specific examples of dyes include Sudan Black SM, First Yellow G, Mouthamine FB, Rhodamine B Lake, Methyl Violet B Lake, Prilianto Green, Oil Yellow GG, Casset YG, and Orazo I Pigments such as carbon black, benzidine yellow, pigment yellow, Indian first orange, irgasin red, barani tonirin red, toiserin red, force min FB, vigmen Toray Orange 1, Lake Red 2G, Phthalocyanine Blue, Vigmentable I, Phthalocyan Anine green and the like, and magnetic powders include magnesite and iron black.
• preferred are a colorant selected from the group consisting of cyan, magenta and yellow dyes and a colorant selected from the group consisting of cyan, magenta and yellow pigments.
• the content of the colorant is usually 2 to 15% by weight, preferably 3 to 10% by weight.
• a wax may be contained together with the toner binder and the colorant.
• Known waxes can be used as the wax of the present invention.
• the wax include polyolefin resins (eg, polyethylene wax and polypropylene wax); long-chain hydrocarbons (eg, paraffin wax, sasol wax); No. Of these, carbonyl group-containing waxes are preferred.
• carbonyl group-containing wax examples include polyalkanoic acid esters (carnaubax, montan wax, trimethylolpropane tribenate, Benyu erythritol tetrabehenate, penyu erythritol diacetate dibenetate, glycerin tribe Henylates, 1,18-octane decanediol-bis-stearate, etc.); polyalkanol esters (tristearyl trimellitate, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide) Etc.); polyalkylamides (such as tristearyl trimellitate); and dialkyl ketones (such as distearyl ketone).
• polyalkanoic acid esters carnaubax, montan wax, trimethylolpropane tribenate, Benyu erythritol tetrabehenate, penyu erythritol di
• carbonyl group-containing resins are polyalkanoic esters.
• the melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 50 to 120 ° C, from the viewpoint of heat-resistant storage stability and cold offset at the time of fixing at a low temperature. 60 to 90 ° C.
• the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 1 to 100 cps, as a value measured at a temperature 20 ° C. higher than the melting point, from the viewpoint of hot offset resistance and low-temperature fixability. 0 to; LOO cps.
• the content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight, and particularly preferably 10 to 25% by weight.
• a charge control agent and a fluidizing agent can be further used.
• Known charge control agents include Nig Mouth Synthetic Dye, quaternary ammonium salt compound, quaternary ammonium base-containing polymer, metal-containing azo dye, salicylic acid metal salt, sulfonic acid group-containing polymer, and fluorine-containing And a halogen-substituted aromatic ring-containing polymer.
• the content of the charge control agent is usually 0 to 5% by weight.
• Known fluidizers such as colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder can be used.
• Dry type toner can be manufactured by the following methods (1) to (3).
• the toner material After dissolving and dispersing the toner material in a solvent in which the toner binder is soluble, the toner material is dispersed in a poor solvent of the toner binder (eg, water, water-methanol) with stirring, and then the solvent is distilled off to form toner particles.
• a poor solvent of the toner binder eg, water, water-methanol
• the solvent is distilled off to form toner particles.
• a method to obtain spherical toner by solid-liquid separation and drying is (3) the dispersion granulation method, and particularly the dispersion granulation method in which the poor solvent serving as the dispersed phase is an aqueous medium.
• a polyester having an isocyanate group and a blocked amine (extender) are used together with other components (low-molecular-weight polyester, pigment, additive, etc.) in an organic solvent.
• a dispersant Used in dispersion granulation in an aqueous medium.
• the agent include ethyl acetate, acetone, and methyl ethyl ketone.
• a dispersant can be used if necessary. Boiling force using a dispersant It is preferable because the particle size distribution becomes sharp and the dispersion is stable.
• dispersant examples include water-soluble polymers (H), organic dispersants such as surfactants (5), and inorganic dispersants (A).
• examples of (H) include nonionic water-soluble polymers (H-1), anionic water-soluble polymers (H-2), and cationic water-soluble polymers (H-3).
• Examples of (HI-1) include polyvinyl alcohol, hydroxyethyl cellulose, polyacrylamide, and modified polyether.
• Examples of (HI-2) include polystyrene sulfonate, polyacrylate, carboxymethyl cellulose soda salt and the like.
• Examples of (HI-3) include quaternary ammonium salts of polystyrene, polyvinylimidazoline hydrochloride, polyallylamine hydrochloride and the like.
• Examples of (/ 3) include sodium lauryl sulfate and sodium oleate.
• Examples of (a) include calcium carbonate powder, calcium phosphate powder, and silica fine powder.
• Two or more dispersants can be used in combination.
• the content of the dispersant is usually from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight.
• the dispersant can be left on the surface of the toner particles. However, it is preferable to remove the solvent and then wash and remove it from the charged surface of the toner. From the viewpoint of easy removal by washing, the dispersant used is preferably an organic dispersant such as a water-soluble polymer ( ⁇ ) and a surfactant (?).
• the dry toner of the present invention may be made of a carrier such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite or the like whose surface is coated with a resin (acrylic resin, silicone resin, etc.) as necessary. Is used as a developer for an electric latent image. Also, instead of the carrier particles, it can rub against a member such as a charging blade to form an electric latent image.
• the dry toner in the present invention is fixed on a support (paper, polyester film, etc.) by various known fixing methods to obtain a recording material.
• the fixing method examples include a thermal fixing method such as an infrared lamp method, a xenon flash method, a planar heating method, a heating roller fixing method, a heat belt fixing method, and a high frequency fixing method: a pressure fixing method: a solvent fixing method, and the like.
• a thermal fixing method such as an infrared lamp method, a xenon flash method, a planar heating method, a heating roller fixing method, a heat belt fixing method, and a high frequency fixing method: a pressure fixing method: a solvent fixing method, and the like.
• a heat fixing method is preferable, a xenon flash method, a sheet heating method, a heating opening fixing method, and a heat belt fixing method are particularly preferable.
• the heat roller fixing method and the heat belt fixing method are particularly preferable. is there. ⁇ Example>
• reaction vessel equipped with a cooling pipe, stirrer and nitrogen inlet pipe, put 224 parts of 2-mol adduct of bisphenol A-ethylene oxide, 276 parts of isophthalic acid, and 2 parts of dibutyltin oxide at normal pressure. At 230 ° C for 8 hours, and then react for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg, then cool to 80 ° C and isophorone disodium in ethyl acetate. The reaction was carried out with 188 parts of benzoate for 2 hours to obtain an isocyanate group-containing prepolymer having a weight average molecular weight of 1200.
• the mixed solution was transferred to a kolben equipped with a stir bar and a thermometer, heated to 98 ° C., the solvent was removed while the urea reaction was being performed, followed by filtration, washing and drying, followed by air classification and granulation. diameter d 5. Yielded 6 ⁇ 111 toner particles. Then, 100 parts of the toner particles and 0.5 part of colloidal silica (Aerosil R 972: manufactured by Nippon Aerosil) were mixed in a sample mill to obtain Toner (1) of the present invention. The practical sphericity of the toner particles was 0.98.
• the toner binder component in the toner (1) has a Tg of 52 ° C and a 7 ⁇ 7 of 123 ° C. 'Is 132 ° (:, peak molecular weights were 4500 and 70,000.
• the number average molecular weight of the high molecular weight polyester (A-1) in the toner binder was 6000, and the weight average molecular weight was 64,000. / MnB was 3.2 and MwA / MwB was 16.
• Tg was 55 ° C
• ⁇ 7 was 128 ° C
• TG ′ was 140 ° (the peak molecular weight was 5000 and 80,000.
• MnA / MnB was 3.3
• MwA / MwB was 17.
• the difference (SPA-SPB) between the SP value (SPA) of (A-2) and the SP value (SPB) of (B-2) in the toner binder was 0.27.
• Tg was 53 ° C
• ⁇ 7 was 123 ° TG 'was 136 ° C
• beak molecular weights were 5,000 and 38,000.
• MnA / MnB was 4.0 and MwA / MwB was 8.3.
• the difference (SPA-SPB) between the SP value (SPA) of (A-3) and the SP value (SPB) of (B-3) in the toner binder was 0.36.
• a toner (3) of the present invention was obtained in the same manner as in Example 2 except that the toner binder (3) was used.
• the practical degree of sphericity of the toner particles was 0.97. Table 1 shows the evaluation results.
• toner binder 354 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of isofluric acid are polycondensed using 2 parts of dibutyltin oxide as a catalyst to obtain a comparative toner binder having a number average molecular weight of 3700 and a weight average molecular weight of 8000 (1 ).
• the toner binder (1) had a Tg of 57 ° C, a Tr? Of 136 ° C, and a TG 'of 133 ° C.
• the peak molecular weight was 8,900.
• Example 1 0.38 20% 1 30 ° C 1 80 ° C 1 14.9 MC / g
• Example 2 0.3 7 1 9% 1 5 0 C 2 3 0 C or more 1 1 5.1 C / g
• Example 3 0.3 7 2 0% 1 30 ° C 1 800 ° C-1 5.5 AC / g
• Example 4 0.3 9 2 0% 1 30 ° C 1 80 ° C-17.3 HCI
• Example 5 0.3 9 2 0% 1 30 ° C 18 0 ° C 1 17.1 AiC / g Comparative Example 10. 3 5 2 1% 1 5 0 ° C 1 6 0 ° C 1 1 5.3 C / g
• the quietness density was measured using Hosokawa Micron powder test Yuichi.
• the residual ratio of toner having better heat resistance storage stability is smaller.
• the oil supply device was removed from the fixing device of a commercially available color copier (CLC-11; manufactured by Canon), and the fixing was evaluated using a modified machine in which the oil on the fixing roll was removed.
• the gloss development temperature was defined as the fixing roll temperature at which the 60 ° gloss of the fixed image became 10% or more.
• the fixing was evaluated in the same manner as in the above GLOS S, and the presence or absence of hot offset to the fixed image was visually evaluated.
• the temperature of the fixing roll at which the hot offset occurred was taken as the hot offset generating temperature.
• 1 g of toner and 24 g of ferrite carrier for electrophotography are mixed for 30 minutes using a turbula shaker mixer, and the charge amount is measured for blow-off charge amount. The measurement was performed using an apparatus (manufactured by Toshiba Chemical).
• the dry toner of the present invention has the following effects.

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• 2000
  • 2000-03-28 DE DE60027837T patent/DE60027837T2/de not_active Expired - Lifetime
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